Curable adhesives

ABSTRACT

A curable adhesive composition comprises a thermoplastic fluoropolymer, an elastomeric fluoropolymer, an ethylene copolymer and a crosslinking component. The composition preferably also comprises a tackifier. The crosslinking component preferably comprises a free radial generator such as a peroxide and a co-crosslinking agent comprising a multifunctional monomer. The adhesive is particularly useful with heat recoverable articles and bonds exceptionally well to fluoropolymer substrates.

BACKGROUND OF THE INVENTION

This invention relates to curable adhesives, a heat recoverable article coated on at least a portion of a surface thereof with said adhesive, and to a method of bonding to a substrate using said adhesive.

The adhesive is particularly useful for bonding to a wide variety of surfaces, including polymeric surfaces having a low surface energy, i.e. a surface energy of less than about 27 dynes/cm, as determined by a measurement of critical surface tension. Such surfaces include, for example, fluoropolymers such as an ethylene-tetrafluoroethylene copolymer or polytetrafluoroethylene. It is well known that it is extremely difficult to bond to such surfaces. In U.S. Pat. No. 4,197,380 to Chao et al a hot melt adhesive capable of bonding to such surfaces is disclosed. The adhesive comprises an ethylene copolymer, a fluoroelastomer and a tackifier in specified proportions. While this adhesive performs satisfactorily in many applications it has been found that under certain demanding conditions greater bond strength and/or sealing performance is desired.

SUMMARY OF THE INVENTION

This invention provides an adhesive composition comprising:

(a) about 30 to about 80% by weight of a thermoplastic fluoropolymer;

(b) about 5 to about 40% by weight of an elastomeric fluoropolymer;

(c) about 5 to about 25% by weight of a thermoplastic ethylene copolymer comprising at least 50 mole% of units derived from ethylene and at least 5 mole % of units derived from at least one unsaturated comonomer containing at least one polar group;

(d) about 1 to about 10% by weight of a crosslinking agent component; and

(e) 0 to about 20% by weight of a tackifier; all percentages by weight being based on the total weight of the five components.

The composition is particularly useful for bonding to a variety of surfaces including, fluoropolymer surfaces such as ethylene-tetrafluoroethylene copolymers and polytetrafluoroethylene. When used to bond to uncrosslinked ethylene-tetrafluoroethylene copolymers it has been found that preferred adhesive compositions of this invention fail cohesively in lap shear tests.

Another aspect of this invention comprises a heat-recoverable article having a coating on at least a portion of a surface thereof, an adhesive composition comprising:

(a) about 30 to about 80% by weight of a thermoplastic fluoropolymer;

(b) about 5 to about 40% by weight of an elastomeric fluoropolymer;

(c) about 5 to about 25% by weight of a thermoplastic ethylene copolymer comprising at least 50 mole% of units derived from ethylene and at least 5 mole % of units derived from at least one unsaturated comonomer containing at least one polar group;

(d) about 1 to about 10% by weight of a crosslinking agent component; and

(e) 0 to about 20% by weight of a tackifier;

all percentages by weight being based on the total weight of the five components.

A further aspect of this invention comprises a method of bonding a surface to another surface, which method comprises:

(i) applying to one of the surfaces to be bonded an adhesive composition comprising:

(a) about 30 to about 80% by weight of a thermoplastic fluoropolymer;

(b) about 5 to about 40% by weight of an elastomeric fluoropolymer;

(c) about 5 to about 25% by weight of a thermoplastic ethylene copolymer comprising at least 50 mole% of units derived from ethylene and at least 5 mole % of units derived from at least one unsaturated comonomer containing at least one polar group;

(d) about 1 to about 10% by weight of a crosslinking agent component; and

(e) 0 to about 20% by weight of a tackifier;

all percentages by weight being based on the total weight of the five components;

(ii) bringing the surfaces to be bonded together with said adhesive positioned between them; and

(iii) applying heat to cause the curable adhesive to melt and flow and to cure the adhesive.

BRIEF DESCRIPTION OF THE INVENTION

FIG. 1 illustrates a soldering device in which the adhesive composition of this invention is used.

FIG. 2 illustrates the device of FIG. 1 installed to form a sealed cable shield termination.

DETAILED DESCRIPTION OF THE INVENTION

Each of the thermoplastic fluoropolymer and the elastomeric fluoropolymer can be a polymer of one or more fluorinated monomers containing ethylenic unsaturation and optionally one or more other compounds containing ethylenic unsaturation. The fluorinated monomer may be a perfluorinated monoolefin, for example hexafluoropropylene or tetrafluoroethylene, or a partially fluorinated monoolefin which may contain other substituents, e.g. chlorine or perfluoroalkoxy, for example vinylidene fluoride, chlorotrifluoroethylene and perfluoroalkyl vinyl ethers in which the alkyl group contains up to six carbon atoms, e.g. perfluoro (methyl vinyl ether); the monoolefin is preferably a straight or branched chain compound having a terminal ethylenic double bond and containing less than six carbon atoms, especially two or three carbon atoms. The polymer preferably consists of units derived from fluorine-containing monomers. When units derived from other monomers are present, the amount thereof is preferably less than 30 mole %, generally less than 15 mole %; such other monomers include, for example olefins containing less than six carbon atoms and having a terminal ethylenic double bond, especially ethylene and propylene. The fluoropolymer is thermoplastic or elastomeric depending on the mole ratio of the monomer(s) used and the process used in its manufacture.

Preferred thermoplastic fluoropolymers are homo- and copolymers of vinylidene fluoride, such as copolymers thereof with hexafluoropropylene. Preferred thermoplastic fluoropolymers are commercially available from Pennwalt under the trademark Kynar, for example Kynar 7201 and Kynar 9301.

The thermoplastic fluoropolymer is present in the adhesive composition in an amount of about 30 to about 80% by weight. Preferably the thermoplastic fluoropolymer is present in an amount of about 35 to about 70% by weight and most preferably of about 40 to about 60% by weight, all percentages being by weight based on the total weight of the five components (a) through (e).

Preferred elastomers are copolymers of vinylidene fluoride and at least one other fluorinated monomer, especially one or more of hexafluoropropylene, tetrafluoroethylene and chlorotrifluoroethylene, the vinylidene fluoride content preferably being 30 to 70mole %. Commercially available fluoroelastomers of this class include copolymers of vinylidene fluoride and hexafluoropropylene such as Viton A, Viton A35 and Viton AHV sold by du Pont; copolymers of vinylidene fluoride, hexafluoropropylene and tetrafluoroethylene such as Viton B and Viton B50 sold by du Pont; and copolymers of vinylidene fluoride and chlorotrifluoroethylene such as Kel-F sold by Minnesota Mining and Manufacturing Co. The Mooney viscosity of the elastomer at 100° C. is generally 20 to 200, preferably 30 to 160.

The elastomeric fluoropolymer is present in the adhesive composition in an amount of about 5 to about 40% by weight. Preferably the elastomeric fluoropolymer is present in an amount of about 10 to about 30% by weight and most preferably of about 15 to about 25% by weight, all percentages being by weight based on the weight of the five components (a) through (e).

The ethylene copolymer is preferably a crystalline copolymer containing at least 50 mole %, preferably at least 60 mole %, especially at least 65 mole % of units derived from ethylene, and at least 5 mole %, preferably 10 to 40 mole %, especially 15 to 35 mole %, particularly 15 to 25 mole %, of units which contain at least one polar group which units may be obtained by copolymerizing at least one unsaturated comonomer containing at least one polar group and/or by modification, e.g. by partial or complete hydrolysis, of units derived from at least one such comonomer. The comonomer preferably contains a terminal ethylenic double bond. Preferred polar groups are carboxyl groups and carboxylic ester groups, including both pendant carboxylic ester groups, derived for example from alkyl esters of unsaturated carboxylic acids, and pendant alkyl carbonyloxy groups, derived for example from vinyl esters of saturated carboxylic acids. Other polar groups include cyano groups and hydroxyl groups, which may be obtained for example by hydrolysis of copolymers containing units derived from vinyl esters. Particularly suitable monomers include vinyl esters of saturated carboxylic acids containing 1 to 4 carbon atoms, especially vinyl acetate; acrylic and methacrylic acids; and alkyl (including cycloalkyl) and aryl esters, especially methyl esters, of acrylic and methacrylic acids, said esters preferably containing at most 10 carbon atoms, especially methyl methacrylate, methyl acrylate and ethyl acrylate.

The copolymer may contain units in addition to those derived from ethylene and those containing polar groups, but the amount of such additional units is preferably less than 20 mole %, particularly less than 10 mole %, especially substantially zero.

Particularly preferred as the copolymer is a copolymer of ethylene and vinyl acetate and 0 to 10 mole % of another comonomer, preferably a polar comonomer. Such copolymers are referred to herein as EVA copolymers. The vinyl acetate content in such copolymers is preferably 20 to 30 mole %. For some purposes an EVA copolymer having a melt index of not more than 10, e.g. 1.5 to 7.5, is preferred.

Suitable commercially available ethylene copolymers include the copolymers of ethylene and ethyl acrylate with a small proportion of methacrylic acid which are sold by Union Carbide as DPD 6169 and DPD 6181 and the 72:28 copolymers of ethylene and vinyl acetate which are sold by du Pont as Elvax 4260 and 260.

The thermoplastic ethylene copolymer is present in the adhesive composition in an amount of about 5 to about 25% by weight. Preferably the ethylene copolymer is present in an amount of about 10 to about 25% by weight and most being by weight based on the total weight of the five components (a) through (e).

The crosslinking component comprises a free radical generator, such as an organic peroxide crosslinking agent of which many are known and commercially available, such as dicumyl peroxide, benzoyl peroxide, and the like. In addition to the free radical generator, a co-crosslinking agent may be present, if desired. The co-crosslinking agent can be a multifunctional monomer capable of crosslinking the particular polymer when initiated by the free radical generator or irradiation. Typically, the co-crosslinking agent contains at least two ethylenic double bonds, which may be present, for example, in allyl, methallyl, propargyl or vinyl groups. Preferred co-crosslinking agents are triallyl cyanurate (TAC), triallyl isocyanurate (TAIC), triallyl trimellitate, triallyl trimesate, tetrallyl pyromellitate, the diallyl ester of 1,1,3-trimethyl-5-carboxy-3-(p-carboxypenyl) indan, or other multifunctional monomers such as N,N'-m-phenylene dimaleimide, or the like. Mixtures of co-crosslinking agents can be used.

The crosslinking component, i.e. the free radical generator and co-crosslinking agent, if present, is present in an amount of about 1 to about 10%, preferably of about 2 to about 8% and most preferably of about 3 to about 6%, all percentages being by weight based on the total weight of the five components.

The term "tackifier" is used in adhesive art to denote a material which when added to an adhesive composition promotes its adhesion to a substrate, by increasing its ability to wet the substrate. Many tackifiers are known. We prefer to use low molecular weight polymers of monomers which contain ethylenic unsaturation and are free of polar groups, for example polymers of one or more compounds of the formula

    R.sub.1 CH═CR.sub.2 R.sub.3

wherein each of R₁, R₂ and R₃, which may be the same or different, is a substituted or unsubstituted alkyl (including cycloalkyl), alkenyl (including cycloalkenyl), aryl, aralkyl or alkaryl radical containing less than ten carbon atoms. Suitable such tackifiers include Nevpene 9500, which is believed to be a copolymer of a mixture of aromatically and alphatically substituted ethylenes, and Piccotex 75, which is believed to be a copolymer of vinyl toluene and α -methylstyrene. Other tackifiers which can be used include terpene-phenolic resins (e.g. Nevillac Hard). The tackifiers used preferably have at least one of the following properties

    ______________________________________     Brookfield Viscosity at 160° C.                          80-1500 centipoises     Ball-and-Ring Softening point                          50-130° C.     Molecular Weight     <3000     ______________________________________

The tackifier is optional in the adhesive composition and if present should be in an amount of less than about 20% by weight. Preferably the composition contains about 5 to about 20% by weight of tackifier and most preferably about 10 to about 15% by weight, all percentages being by weight based on the total weight of the five components (a) through (e).

The adhesive may contain additional additives such as stabilizers, flame retardants, pigments, fillers and the like. Generally, additives are present in a total amount of less than about 10% by weight, based on the weight of the total composition (i.e. the total weight of components (a) through (e) plus additives).

The adhesive composition of this invention is particularly advantageous for sealing and/or bonding to a surface having a low surface energy, i.e. a surface energy of less than about 27 dynes/cm. Examples of such surfaces are ethylene tetrafluoroethylene copolymer, polytetrafluoroethylene, and the like. The polymer may be crosslinked or uncrosslinked. The adhesive is generally applied to one of the surfaces to be bonded together and then the surfaces to be bonded are brought together with the adhesive positioned between them. Heat is applied to cause the adhesive to melt and flow to fill any irregularities in the surface and the assembly is then cooled. The adhesive exhibits excellent sealing between the surfaces and in the case of eylene-tetrafluoroethylene copolymer surfaces, even if uncrosslinked, exhibits excellent bonding to the surface. The adhesive can, of course, be used with surfaces with higher surface energies and thus much easier to bond to. Such other surfaces include polymeric and metallic surfaces.

In a preferred embodiment, the adhesive is coated on at least a portion of a surface of a heat recoverable article, such as a heat recoverable tubular article or wraparound sleeve. Typically the article is heat shrinkable and the adhesive is coated on at least a portion of the inner surface thereof or is provided as a preformed adhesive insert.

Heat-recoverable articles are articles the dimensional configuration of which may be made substantially to change when subjected to heat treatment.

Usually these articles recover, on heating, towards an original shape from which they have previously been deformed but the term "heat-recoverable", as used herein, also includes an article which, on heating, adopts a new configuration, even if it has not been previously deformed.

In their most common form, such articles comprise a heat-shrinkable sleeve made from a polymeric material exhibiting the property of elastic or plastic memory as described, for example, in U.S. Pat. Nos. 2,027,962; 3,086,242 and 3,597,372. As is made clear in, for example, U.S. Pat. No. 2,027,962, the original dimensionally heat-stable form may be a transient form in a continuous process in which, for example, an extruded tube is expanded, whilst hot, to a dimensionally heat-unstable form but, in other applications, a preformed dimensionally heat-stable article is deformed to a dimensionally heat-unstable form in a separate stage.

In the production of heat-recoverable articles, the polymeric material may be cross-linked at any stage in the production of the article that will enhance the desired dimensional recoverability. One manner of producing a heat-recoverable article comprises shaping the polymeric material into the desired heat-stable form, subsequently cross-linking the polymeric material, heating the article to a temperature above the crystalline melting point or, for amorphous materials the softening point, as the case maybe, of the polymer, deforming the article and cooling the article whilst in the deformed state so that the deformed state of the article is retained. In use, since the deformed state of the article is heat-unstable, application of heat will cause the article to assume its original heat-stable shape.

The adhesive composition is particularly useful in heat recoverable articles such as harnesses, transition, boots, sleeves for sealing wire or cable splices or the like. The heat recoverable article can be of any suitable polymeric material. Preferred articles are comprised of polyethylene, polyvinylidene fluoride, blends of vinylidene fluoride polymers, polyamides or polyesters or other thermoplastic polymer capable of being rendered heat recoverable. Such materials may be crosslinked.

Heat-recoverable articles with which the adhesive composition of this invention can be used are well known. Certain of said articles can be used for forming solder connections between electrical conductors in view of the ease of forming the connection and the quality of the connection so formed. For such applications the article, usually in the form of a sleeve, contains a quantity of solder for forming the electrical connection and a pair of fusible inserts for sealing the connection. These articles are described for example in U.S. Pat. Specification Nos. 3,243,211, 4,282,396, 4,283,596 and 4,722,471, European Patent Publication No. 0,270,283, and British Patent No. 1,470,049 the disclosures of which are incorporated herein by reference, and are sold by Raychem Corporation, Menlo Park California under the trade mark "SOLDER SLEEVE" amongst others. Similar articles are also disclosed in U.S. Pat. Nos. 4,504,699 and 4,282,396, which disclosures are also incorporated herein by reference.

A typical heat recoverable soldering device is shown in the accompanying drawing. In FIG. 1 of the drawing, a heat recoverable soldering device 10, comprises a heat recoverable sleeve 11 and is provided with solder insert 12 and adhesive inserts 14 and 16, each of the curable adhesive formulation of this invention. In FIG. 2, shielded cable 20 is insulated with uncrosslinked ethylene-tetrafluoroethylene copolymer (commercially available as Tefzel from du Pont). The insulation 22 has been removed to expose a portion of the metallic braid 24, which acts as the cable shield. Ground lead 26 is secured to the braid by solder 12 of the recovered soldering device 10. The adhesive inserts 14 and 16 seal the open ends of the recovered sleeve 11.

When used in such a soldering device, or other heat shrinkable tubular article the adhesive is coated on the inner surface of the tube so that when it recovers, the adhesive comes into contact with the substrate. As the article is heated to cause it to recover, the adhesive melts and flows to fill any voids between the article and the substrate and cures. The cured adhesive seals the open end of the article and bonds to the substrate. The adhesive bond formed by the cured adhesive exhibits exceptional bond strength, even when bonded to a surface with low surface energy. With a surface of uncrosslinked ethylene-tetrafluoroethylene copolymer the bond is sufficiently strong that in a lap shear test the bond fails cohesively rather than adhesively. With a surface of polytetrafluoroethylene, the bond is less strong but an effective seal is obtained.

The following examples illustrate adhesive formulations in accordance with this invention and use of an adhesive of this invention in a heat recoverable article.

EXAMPLES 1-7

Adhesive formulations having the ingredients and amounts thereof specified in Table I were prepared by mixing the ingredients in a Brabender at 60 rpm for approximately 10 minutes at 110° C.

                                      TABLE I     __________________________________________________________________________                1   2   3   4   5   6   7     __________________________________________________________________________     PVDF       57% 55% 53% 55% 53% 55% 53%     Ethylene Copolymer                12.5%                    12.5%                        12.5%                            12.5%                                12.5%                                    12.5%                                        12.5%     Fluoroelastomer                10% 10% 10% 10% 10% 10% 10%     Tackifier #1                5%  5%  5%  5%  5%  5%  5%     Tackifier #2                10% 10% 10% 10% 10% 10% 10%     Xlinking Agent                3%  3%  3%  3%  3%  5%  7%     Co-Xlinking Agent #1                --  2%  4%  --  4%  --  --     Co-Xlinking Agent #2                --  --  --  2%  --  --  --     Misc. Additives                2.5%                    2.5%                        2.5%                            2.5%                                2.5%                                    2.5%                                        2.5%     __________________________________________________________________________      PVDF = A thermoplastic terpolymer of vinylidene fluoride,      tetrafluoroethylene and hexafluoropropylene, commercially available as      Kynar 9301 from Pennwalt.      Ethylene Copolymer = a copolymer of ethylene and vinyl acetate containing      28% vinyl acetate, commercially available as Elvax 4260, commercially      available from du Pont.      Fluoroelastomer = a copolymer of vinylidene fluoride and      hexafluoropropylene (Molar ratio 60:40) commercially available as Viton A      35 from du Pont.      Tackifier #1 = a copolymer of vinyltoluene and α-methyl styrene      having a softening point of 75° C., commercially available as      Piccotex 75 from Hercules.      Tackifier #2 = a copolymer of vinyltoluene and α-methyl styrene      having a softening point of 120° C., commercially available as      Piccotex 120 from Hercules.      Crosslinking Agent = 2,5dimethyl, 2,5di(t-butyl peroxy) hexyne3,      commercially available as Luperco 130 XL from Pennwalt.      Co-crosslinking Agent #1 = N,N'-mphenylenedimaleimide, commercially      available from du Pont.      Co-crosslinking Agent #2 = triallylisocyanurate.

EVALUATION

The adhesive formulation prepared in Example 2, was used as an adhesive insert in a heat recoverable soldering device as shown in FIG. 1, discussed above. Twenty-five samples were prepared and installed as in FIG. 2.

The installed devices were tested as follows:

Moisture Resistance Test: The samples were tested using Mil Std. 202, Method 106 which is a 10 day temperature cycling (-10 to 65° C.) test conducted at 95% humidity. Insulation Resistance Test: The twenty-five samples were tested using MIL-S-83519. Within one hour from the time they were removed from the humidity test, the samples were immersed in a salt and water-wetting agent solution for 30 minutes. While the samples were still immersed, a voltage of 500 volts DC was applied between the ground lead and the water bath. An ohmmeter is used to measure the resistance of the sealing sleeve. If the measured resistance is 1000 megaohm or greater the sample passed the test. All samples passed. The test was then extended beyond the method of MIL-S-83519. The samples remained immersed for an additional 30 minutes and then a voltage of 1000 volts DC was applied. The resistance was again measured. All samples had a resistance of at least 1000 megaohm.

Lap Shear Test: Heat recoverable, tubular soldering devices were prepared, each having solder inserts made from one of the above formulations. Each device was installed over a cable having an uncrosslinked Tefzel (ethylene-tetrafluoroethylene copolymer) jacket, each cable having been cut in half at the mid-point with a diagonal cut. A reinforcing heat recoverable sleeve was installed over the device to prevent splitting of the heat recoverable sleeve of the device. The ends of the cable were pulled opposite directions in an instron at a crosshead speed of 10 mm/min. The results are shown in Table III and compared to a control sample in which the adhesive formulation contained no crosslinking component.

                  TABLE II     ______________________________________     Sample No.   Bond Strength (psi)     ______________________________________     1            339     2            432     3            464     4            403     5            338     6            449     7            462     Control      320     ______________________________________

It was noted that the samples containing the crosslinking component exhibited cohesive failure. 

What is claimed is:
 1. An adhesive composition comprising:(a) about 30 to about 50% by weight of a thermoplastic vinylidene fluoride homopolymer or copolymer; (b) about 5 to about 40% by weight of an elastomeric vinylidene fluoride; (c) about 5 to about 25% by weight of a thermoplastic ethylene copolymer comprising at least 50 mole% of units derived from ethylene and at least 5 mole % of units derived from at least one unsaturated comonomer containing at least one polar group; (d) about 1 to about 10% by weight of a crosslinking agent component; and (e) 0 to about 20% by weight of a tackifier; all percentages by weight being based on the total weight of the five components.
 2. An adhesive composition in accordance with claim 1, wherein (a) is polyvinylidene fluoride.
 3. An adhesive composition in accordance with claim 1, wherein (a) is a thermopolastic copolymer of vinylidene fluoride and at least one other monomer.
 4. An adhesive composition in accordance with claim 3, wherein (a) is a thermoplastic terpolymer of vinylidene fluoride, tetrafluoroethylene and hexafluoropropylene.
 5. An adhesive composition in accordance with claim 1, wherein (b) is an elastomeric copolymer of vinylidene fluoride and at least one other monomer.
 6. An adhesive composition in accordance with claim 1, wherein (b) is an elastomeric copolymer of vinylidene fluoride and hexafluoropropylene.
 7. An adhesive composition in accordance with claim 1, wherein (c) is an ethylene-vinyl acetate copolymer.
 8. An adhesive composition in accordance with claim 1, wherein (d) is 2,5-dimethyl, 2,5-di(t-butylperoxy) hexyne-3.
 9. An adhesive composition in accordance with claim 1, wherein (d) is a mixture of 2,5-dimethyl, 2,5-di(t-butylperoxy) hexyne-3 and triallyl isocyanurate.
 10. An adhesive composition in accordance with claim 1, wherein (d) is a mixture of 2,5-dimethyl, 2,5-di(t-butylperoxy) hexyne-3 and N,N'-m-phenylenedimaleimide.
 11. An adhesive composition in accordance with claim 1, wherein (c) is present in an amount of about 5 to about 20% by weight.
 12. An adhesive composition in accordance with claim 11, wherein (e is a copolymer of vinyl toluene and α-methyl styrene. 